Process for the continuous production of brown water-insoluble azo-dyestuffs on fabrics of vegetable fibers



4 Claims. (or. 8-46) For the production of brown water-insolubleazo-dyestuffs. by the methods of the ice color technique there aremainly used arylamides of heterocyclic o-hydroxy-' carboxylic acids incombination with diazonium com- 1 pounds from primary amines of thebenzene series. The arylamides of 3-hydroxy-diphenyleneoxide-Z-carboxylic acid and 2-hydroxy-carbazole-3-carboxylic acid whichpermit the production of very fast brown tints are of particularimportance. Some products of this series, therefore, are used for sometime on an industrial-scale for the production of brown dyeing-s onvegetable fibers,

for example l-(3'-hydroxy-diphenyleneoxide-2'-carboylamino)-2.5-dimethoxybenzene (Naphtol AS-BT) or 1- (2'hydroxy carbazole 3' carboylamino) 4 chloroatet Patented May 11, 1965cases they do not possess a constant tint and are not dyestuffs can beproduced in a continuous manner on benzene (Naphtol AS-LB) (cf. K.Venkataraman, The

that especially the coupling components used must fulfill certainrequirements as a prerequisite for their practical application. As oneof these requirements, the material treated with .the coupling componentshall have a 1 high stability during the drying operation following theimpregnation, in order to dry the material at a tempera- .ture as highas possible thus shortening the drying process. Furthermore, thematerial treated with the coupling component shall have a good wettingproperty so that the development with the diazonium compound can beconducted rapidly and the speed of the goods can be kept as high aspossible. Furthermore, the coupling energy of the coupling componentused shall be high and finally, the developed dyeings shall rapidlyattain the final tint, when they are subsequently soaped, requirementswhich must also be met with regard to a rapid passage of the goods.

The arylarnides of S-hydroxy-diphenylene oxide-2% carboxylic acid andZ-hydroxycarbazole-Ibcarboxylic acid, Naphtol AS-BT and Naphtol AS-LB,which are known for a long time and used in the industry, only partlyfulfill these requirements for continuously pro- .ducing the dyestuffson the foulard. The impregnations prepared with these compounds do notpossess the necessary stability to temperatures ranging from 150480" C,

as they are lately used in hot air driers. Furthermore, the couplingenergy is often insufiicient or the production of the final tintrequires very much time so that an economical dyeing process is notpossible. 7 Finally, the dyeings produced on piece goods with thecoupling components hitherto used include the drawback that in manyaromatic amine.

fabrics of vegetable fibers by treating the fabric at a speed of 40 to90 meters per minute, at a temperature between and 95 C., with thealkaline solution of l (3' hydroxy diphenylene oxide 2' carboylamino)-Z-ethoxybenzene and drying it at a temperature between .130 and 180 C.,then developing the dyestuff at a temperature between 15 and 25 C. andat a pH-value between 4 and 6.5 with the diazonium compound from aprimary aromatic amine, passing the material through air for 20-30seconds, then treating it at a temperature between 20 and 60 C. with anaqueous alkali metal carbonate or bicarbonate solution of 0.5 to 2%strength, rinsing, soaping with a detergent for 30-60 seconds at atemperature between and C. and drying it.

The process of the present invention is carried out in such a mannerthat fabrics of vegetable fibers, for example of cotton or regeneratedcellulose, are padded on a foulard, for example a twoor three-rollerfoulard having a color box of a volume as small as possible, at a speedof goods of about 50 to 90 meters per minute at about '85" to C., withan alkaline solution of 1-(3'- hydroxy-diphenyleneoxide-2'-carboylamino) 2 ethoxybenzene, preferably a solution renderedalkaline with sodium hydroxide, then squeezed off to a ratio of liquorof about 60 to and dried at about to C., preferably on a hot air drier.The dyestulf is then developed at a temperature between 15 and 25 C. and

a pH-value between 4 and 6.5 on a twoor three-roller foulard with adiazonium compound from a primary As diazonium compounds there may beused diazonium chlorides, diazonium sulfates, diazonium borofluorides.diazonium chloride-zinc chloride double salts and diazonium naphthalenedisulfonates from primary aromatic amines of the benzene, azobenzene andanthracene series, for example diazonium compounds from1-amino-2-methyl-S-nitrobenzene, l-amino- 2,5-dichlorobenzene,1-amino-2-chloro-5-methoxy-4-benzoylamino-benzene, l-amino-3,5bis-trifiuorornethylbenzene, 1 amino 4 chloro 2 trifluoromethylbenzene,1- amino 2 chloro 5 trifiuoromethylbenzene, 1 amino- 2-chlorobenzene,l-amino-4-nitrobenzene, l-amino-Z- methoxyl-nitrobenzene,l-amino-Z-methyl-4-chlorobenzene, l amino 2 methyl 5 chlorobenzene, lamino- 2-methyl-3-chlorobenzene, 1-amino-2-methoxy-benzene- 5-sulfonicacid-n-butylamide, l-amino-2-methoxybenzene- S-sulfonic aciddiethylamide, l-amino-2,4-dimethyl- S-benzoylaminobenzene,2-amino-4-chlor0-diphenyl ether, 2-amino-4,4-dichlorodiphenyl ether orl-aminoanthraquinone.

When the development with the diazonium compound is complete, thematerial is passed for about 20 to 30 seconds through air and thenafter-treated at 20 to 60 C. with an aqueous alkali metal carbonate orbicarbonate solution containing, per liter of water, about 5 to 20 gramsof an alkali-metal carbonate or bicarbonate, for example sodiumcarbonate or sodium bicarbonate, in order to complete the coupling. -Thematerial is then aisaisr 3 rinsed hot and cold and soaped for 30 to 60seconds, at a temperature between 70 and 90 C., on a full width washingmachine with a washing or dispersing agent, for example soap or a fattyalcohol polyglycol ether, an alkylphenol polyglycol ether or analkylnaphthol polyglycol ether and a small amount of sodium carbonate,whereby the tint is not or only slightly changed. The material is thenrinsed and dried.

The process of this invention avoids the disadvantages hitherto involvedwith the use of the commercial coupling components. When1-(3'-hydroxy-diphenylene oxide-2'- carboylamino)-2-ethoxybenzene isused as coupling component, impregnations can be prepared which are vefystable during drying and possess a very good wetting capacity. Moreover,the dyeings attain very rapidly the final tint when they are soaped sothat the process c: n be carried out at a very high speed of goods.

The brown, khaki and olive dyeings obtainable by this invention possessa very constant tint and very good properties of fastness; particularlyeven the light tints possess a good fastness to light. The dyeings aredischargeable to a White and are, therefore, very suitable in thetextile printing for the production of discharge grounds. Furthermore,they are resistant to a further processing and, therefore, the materialprovided with these dyeings can be easily given a resistance tocreasing.

The following examples serve to illustrate the. invention but they arenot intended to limit it thereto.

Example 1 A mercerized cotton fabric was padded at 90 C. on the foulardat a speed of goods of 45 meters per minute, with the solution describedbelow and squeezed off to a'ratio of liquor of 60%.

3.2 grams of 1-(3-hydroxy-diphenylene oxide-2'-carboylamino) 2-ethoxybenzene, dissolved in 6.4 cc. of denatured ethyl alcohol, 9.5 cc.of water and 1.6 cc. of sodium hydroxide solution of 32.5% strength werestirred into a solution containing, per liter of water, 3 grams of acondensation product of fatty acids of high molecular weight and proteindegradation products, and cc. of sodium hydroxide solution of 32.5%strength. The material was then dried on a hot air drier at 165 to 175C. and the dyestuff was developed at C. with a diazo solutioncontaining, per liter of water, the diazonium compound from 2.5 grams of1-amino-3,5-bis-trifiuoromethylbenzene and 2 grams of the reactionproduct from about 20 mols of ethylene oxide and 1 mol of octadecylalcohol, and 7.5 cc. of acetic acid of 50% strength and having apH-value of about 4. After an air passage for seconds, the material wastreated at 60 C. with a solution containing 10 grams of sodiumbicarbonate per liter of water, rinsed, soaped for 30 seconds at 90 C.with a solution containing, per liter of water, 1 gram of a reactionproduct from 10 mols of ethylene oxide and 1 mol of isododecyl phenoland 3 grams of sodium carbonate, rinsed again and dried.

A yellowish brown dyeing was obtained.

Example 2 Mercerized cotton sateen was padded at 95 C. on th foulard, ata speed of goods of 50 meters per minute, with the solution describedbelow and squeezed off.

7.46 kilograms of 2-(3'-hydroxy-diphenylene oxide-2'-carboylaniino)-2-ethoxybenzene were made into a paste with 1.81kilograms of Monopole Brilliant Oil, mixed with 14.2 liters of sodiumhydroxide solution of 38 B6. and made up with hot water to 1000 liters.

The material was then dried at 165 to 180 C. on the hot flue and thedyestutf was developed at 20 C. with a diazo solution containing in 380liters of water 13.6 kilograms of the diazonium compound from 1-amino-2-methyl-4-benzoylamino-S-chlorobenzene, 3.62 kilograms of a reactionproduct from about 20 mols of ethylene oxide and 1 mol of octadecylalcohol and 7.26 kilograms of acetic acid of 50% strength and having apH-value of about 4.5. After an air passage for 30 seconds. the materialwas treated with a solution containing 4.5 kilograms of sodium carbonatein 378 liters of water, rinsed with water at 70 C., soaped for 50seconds at C. with a solution containing per liter of water 1 gram of areaction product from 10 mols of ethylene oxide and 1 mol of isododecylphenol, rinsed hot and dried.

A yellowish brown dyeing was obtained.

The following table indicates a number of further water-in-solubleazo-dyestutfs which were produced by this invention on fabrics ofvegetable fibers by using the same coupling component and other diazocomponents, and also the tints of the dyeings.

Diazo component Tint 1-arniuo-4-chloro-2-tritluoromethylbenzene Yglowishorange rowu.

Yellowlsh krown.

Bluish brown.

o. Yellowish brown.

l-amino-QAliloro-5-trifluoromethylbenzene. l-amino-z chlorobenzene1-arnino4-nitrobcuzene 1amino-Z-rnethoxwl-nitrobenzene1-amino-2met'hyl-4-chlorobenzen l-arnino-LLmetl\yl-5-chl0robeuzene.l-amino-2-mctllyl-3-chlorobenzenc. l-aiuino-l-methoxybenzene-.i-sultonlcacid-u-butylamide. 1-amiuo-Z-methoxybeuzeue-asulfonic acid-diethyl- Do.Reddish brown.

We claim:

1. Process for the continuous production of brown, water-insolubleazo-dyestuffs on fabrics of vegetable fibers which comprises treatingthe fabric at a speed of goods of 40 to 90 meters per minute, at atemperature between 65 and C., with an alkaline solution of1-(3-hydroxy-diphenylene oxide-2'-carboylamino)-2-ethoxybenzene anddrying it at a temperature between and C., then developing the dyestuifin the fabric at a temperature between 15 and 25 C. and at a pH between4 and 6.5 with a diazonium compound of a primary aromatic amine, passingthe fabric through air for 20 to 30 seconds, then treating it at atemperature between 20 and 60 C. with an aqueous solution of 0.5 to 2%strength of an alkali selected from the group consisting of alkali-metalcarbonates and alkali-metal bicarbonates, and subjecting it to rinsing,soaping with a detergent for 30 to 60 seconds at a temperature between70 and 90 C. and drying.

2. A process as defined in claim 1 in which the alkali is sodiumcarbonate.

3. A process as defined in claim 1 in which the alkali is sodiumbicarbonate.

4. A process as defined in claim 1 in which the detergent is a reactionproduct of ethylene oxide on isododecylphenol.

References Cited by the Examiner UNITED STATES PATENTS 2,032,463 3/36Bergdolt et al. 8-46 2,845,326 7/58 Streck 846 3,029,122 4/62 Posselt etal 846 OTHER REFERENCES Venkataraman: The Chemistry of Synthetic Dyes,vol. 1 PP- 652, 653, 658, and 668-672.

Colour Index, vol. 2, 2nd ed., 1956, The Soc. of Dyers and Colourists,pp. 2569-2570.

NORMAN G. TORCHIN, Primary Examiner. ABRA AM H. WINKELSTEIN, Examiner. i

1. PROCESS FOR THE CONTINUOUS PRODUCTION OF BROWN, WATER-INSOLUBLEAZO-DYESTUFFS ON FABRICS OF VEGETABLE FIBERS WHICH COMPRISES TREATINGTHE FABRIC AT A SPEED OF GOODS OF 40 TO 90 METERS PER MINUTE, AT ATEMPERATURE BETWEEN 65* AND 95*C., WITH AN ALKALINE SOLUTION OF1-(3''-HYDROXY-DIPHENYLENE OXIDE-2''-CARBOYLAMINO)-2-ETHOXYBENZENE ANDDRYING IT AT A TEMPERATURE BETWEEN 130* AND 180*C., THEN DEVELOPING THEDYESTUFF IN THE FABRIC AT A TEMPERATURE BETWEEN 15* AND 25*C. AND AT APH BETWEEN 4 AND 6.5 WITH A DIAZONIUM COMPOUND OF A PRIMARY AROMATICAMINE, PASSING THE FABRIC THROUGH AIR FOR 20 TO 30 SECONDS, THENTREATING IT AT A TEMPERATURE BETWEEN 20* AND 60*C. WITH AN AQUEOUSSOLUTION OF 0.5 TO 2% STRENGTH OF AN ALKALI SELECTED FROM THE GROUPCONSISTING OF ALKALI-METAL CARBONATES AND ALKALI-METAL BICARBONATES, ANDSUBJECTING IT TO RINSING, SOAPING WITH A DETERGENT FOR 30 TO 60 SECONDSAT A TEMPERATURE BETWEEN 70* AND 90* C. AND DRYING.